Electrochemical conversion of hydrocarbons



April 24, 1951 c. H. SCHLESMAN 2,550,089

ELECTROCHEMICAL CONVERSION OF HYDROCARBONS Filed Aug. 31, 1946 4 Sheets-Sheet 2 INVENTOR CA FZLETON H,ScHLEsM/w. BY

Ap 2 1951 c. H. SCHLESMAN 2,550,089

ELECTROCHEMICAL CONVERSION OF HYDROCARBONS Filed Aug. 31, 1946 4 Sheets-Sheet 4 g PULSE {9 elm/596,701,, 0504mm? F/A/AL M0001 A7 70/? COHXIHL OUTPUT TRIGGER P0155 1 @7 F J86 k Q Q 500 sec. g x

92976, law/4e 77/ 5 F0165 E i g L F5 INVENTOR Cameron H. SCHLESMAN.

Patenteci Apr. 24, 1951 UNITED STATES ELECTROCHEMICAL CONVERSION OF HYDROCARBONS Carleton n. Schlesman, Camden, N. 1., assignor to Socony-Vacuum Oil 'companmjlncorporatecl, a corporation of New York Application August e1, 1946,- Serial N0. 694,387

4 Claims. I

This invention relates to chemical reactions and more particularly to chemical reactions which are initiated, induced, accelerated, controlled or otherwise affected by the application of electrical energy to the reaction system;

The effects of heat on chemical reactions are fairly well understood. The temperature and the length of exposure of the reactants to heat are customarily controlled to obtain the desired reaction or rate of reaction. The effect of electricity on ionizable solutions is also fairly well understood. Enough is known about catalysts to make them useful for many purposes. Yet with all this knowledge there are many desirable reactions that cannot be accomplished, or can-- not be efficiently accomplished.

The purpose of this invention is toprovide a new process for chemical reactions, or .a new driving force for chemical reactions, that will permit the accomplishment of reactions that have not heretofore been performed and the 'accom plishment of already known reactions with great er efficiency.

In general, the new process of. chemical reaction is applicable to the reaction of compounds in a gaseous or vapor state although the principle may advantageously be applied, in some instances,' to reactions between compounds in liquid or solid state or even between compounds in different states. I I

The pressure at which the new process may be conducted is subject to extremely. wide variation dependent upon the particularreaction it is desired to accomplish and the various parameters of the system. Pressures of the order of one micron of mercury have beenfound desirable in some instances, while atmospheric pressure or above has been successfully used in others. Nevertheless, pressure does have an important effeet and it is highly desirable that for each particular reaction a pressure be selected at which that reaction proceeds efiiciently.

The temperature, in most reactions thus far conducted, has been around room temperature at the. beginning of the reaction and has risen somewhat in the course of the reaction. It is to be understood, however, that the course of the reactions involved are often materially affected by temperature in the same manner as in ordinary chemical reactions and hence it is within the scope of this invention to control the temperature at the beginning, and during the course of, the reactions, either at a lower or higher level than would exist if the reactants were merely introduced at room temperature and the temperature permitted to change in whatever manner the process caused it to change.

ill

2 in accordance with the principles of this invention are numerous. A few examples are:

(-1) Hydrogenation or dehydrogenation of organic compounds (2) Cracking of organic compounds (3) Polymerization of organic compounds The principles of this invention may be ap-' plied to any chemical reaction in which the degree of control possible with this process is desirable and the course of which is susceptible to being influenced by the application of electrical energy thereto. 7 A I In many instances the reaction may be addi tionally assisted or side reactions lessened in known manner by the use of appropriate catalytic material. Such catalyst may, for example, be suspended in the reaction mixture or the electrodes used for applying the electricalenergy may themselves be made of a catalytic material.

The new process comprises broadly the affect-,

ing of chemical reactions by the application of electrical energy and the control of the eaction by the limiting of the period or periods of application to very short lengths of time, for eX- ample, of the order of a microsecond. Thus, the electrical energy is applied in the form of one or more very short bursts or impacts or pulses. By control of and proper adjustment of the time period of the energy application, the desired re-' actioncan be caused to occur without at the same time causing undesired secondary reactions that will destroy the desired product or form undesired by-products. I

According to the principles of the present in" vention, it has been found that electrical energy can be applied in a novel manner to produce a new and highly desirable result. Previously, electrical energy has been supplied to reactions in a manner analogous to the usual application of heat, and which, with respect to the kinetics of the reactions involved, is essentially continuous. Thus, there was often no way of accomplishing a desired reaction and preventing an undesired one that normally accompanied it. Now el'ectri cal energy is to be supplied in one or more pulses 0r bursts or impacts so short in duration that the desired reaction may be completed thereby with out at the same time gaving the undesired reaction a chance to complete itself. More usually, these pulses may be considered to condition the reactant or reactants for the desired reaction, but not the side reaction, and the desired reaction is then permitted to proceed in the absence. or substantial absence of the conditioning energy. or with a second electrical energy level of substantially lower intensity.

It has been found that when electrical energy is continuously applied .to cause reaction and the reaction permitted to complete itself in the presence of such continuously applied energy, that the reaction often proceeds further than is desired, often produces undesired by-products and sometimes the reaction is entirely different from what is desired. When the same reactant or reactants are caused to react by one or more extremely short applications of energy, the reaction frequently follows an entirely different course, often with more desirable results. Further variations in reaction course may arise from the use of rest periods of relatively long duration between successive energy bursts, during which rest periods electrical energy may be substantially absent or of controlled low intensity, or by the use of single bursts followed by appropriate rest periods, as above.

By short periods of application of the electrical energy is meant a technique for the application of energy in pulses of microsecond duration. It has been found that the course of the reaction is directly dependent upon the duration of this pulse. In some reactants a pulse of 0.1 microsecond duration will be found advantageous whereas other reactants will require pulses of many microseconds for optimum yield.

When a rest period is employed following the application of a pulse the rest period is in every instance many times the length of the pulse. Preferably, it will be at least a thousand times the length of the pulse.

During the rest period there may be a complete absence of any supply of electrical energy to the reactants, but in some instances it may be desirable to continue, during the rest period to supply a relatively low level holding or ionizing energy to the reactants. Such holding or ionizing energy will, if supplied, be'far less in strength than the pulse energy but will serve to facilitate the reestablishment of the flow of pulse energy and also facilitate the completion to the desired degree of the reaction initiated by the pulse energy.

. The energy applied from electrical sources during the course of the reaction commonly takes the form of electromagnetic radiation induced.

between an electrode system within the reactor or electromagnetic radiation propagated into space with such directional characteristics that a powerful field is set up within the reactor.

Such a radiation may be supplemented by conduction currents for purposes of control which take the form of electron streams within the reactor and ion currents between the electrodes. The crest or peak potential of the energy dependent upon the particular reactants under treatment will necessarily be such as toimpart the necessary energy to the particular reactant or reactants under treatment. In general it will be of the order of hundreds of volts. 7

It will be appreciated that the wave form or pulse shape is of equal importance to the factors such as crest voltage and pulse shape in directing the course of the reaction. It is. within the scope of this invention to adjust eachof the factors discussed above to fit it to the particular reaction which it is desired to perform,

This new process is applicable to many different types offreactions. Reactions selected to illustrate the present inventionare the conversion of methane into acetylene, methane into hydrogen, methane into ethane, and methane into ethylene.

'A more complete understanding of this invention may be had fromthe" following detailed description when considered with the drawings, in which:

Figure 1 is a diagrammatic illustration of an electronic reactor shown in vertical section;

Figure 2 is a group of curves showing the energy pulse characteristics.

Figure 3 is a diagrammatic illustration of a modified form of electronic reactor shown in vertical section;

Figure 4 is an electrical circuit diagram showin the manner in which energy is supplied to the reactor of Figure 3;

Figure 5 is a diagrammatic illustration of another modification of the electronic reactor shown in vertical section;

Figure 6 is a schematic block diagram of the elements comprising the pulse generator shown in Figure 5;

Figure '7 is a current-time curve showing a square wave pulse that is suitable for use in applying energy to the reactor; and

Figure 8 is a voltage-time curve showing a radar type pulse.

Referring to the drawings in detail, particularly Figure 1, there is shown an electronic reactor. The electronic reactor comprises a cylindrical side wall I0 and end closure elements II and I2. Elements I I and I2 may be formed of metal, and element I0 of rubber, glass, quartz, a phenolic condensation product, or any other suitable insulating material. If desirable in certain arrangements this may be reversed. Elements II and I2 have secured to their inner faces electrodes I3 and I4 respectively. These electrodes may be formed of brass, copper or other suitable material. Electrical connection is made to the top electrode I3 by means of a conductor I5 that maybe a copper or brass pipe or tubing which also serves as a reactant inlet. Interposed between the copper tube I5 and electrode I3 is a funnel shaped link I6 that is also formed of suitable electrical conducting material such as copper or brass. Electrical connectionis similarly made to electrode I4 by means of pipe I8, which also serves as a product outlet, and the funnel shaped element I9. Electrodes I3 and I4 are provided with a plurality of holes 20 which serve as passageways through which reactants in gaseous state are admitted to and products discharged from the reaction zone IT. The vertical spacing of electrodes I3 and I4 is a function of potential,

' pressure and reactants.

Electrical power in the form of pulses is supplied to the electrodes I3 and I4 by means of a condenser 2I which is connected across them by conductors 22 and 23. The capacity of condenser 2I is quite low and may range from .05 to 5 microfarads. Condenser 2| is continually charged through the resistance 24 and conductors 25 and 26 by a direct current power source not shown. The direct current voltage of the power source may range from 400 to 4000 volts.

A striking electrode 21 is shown suspended from the top, electrode I3. Striking electrode 21 is a small inductance formed. of a material such as that known by the trade name -Nichrome and functions to reduce the voltage required to initiate a discharge between the electrodes I3 and I4. By making the striking electrode 21 in the form of an inductance there will not be an appreciable current drain from electrode I3 which would tend to reduce the discharge voltage between the main electrodes I3 and I4.

Although .the use of electrode 21 is desirable the apparatus can be successfully operated without it. Additionally in some instances the condenser 2| can be eliminated by regulating the capacity formed by the electrodes l3 and M.

The characteristics of the electrical pulses sup- A The above results were obtained from a single pass through the reactor. Substantially complete conversion can be efiecte'd by recycling the unconverted methane.

plied to the electrodes l3 and M are shown in 5 The effect of changing the variables of the re- Figure 2. Curve I, which represents the variation actor on the above reaction isillustrated by the of current flow from condenser 2| with time. is following tabulated results:

(1) (2) 5 4) (5) 5) (7) 8) 9) (10) (11) c2) l 1= c tPCt Retctim Pk. 5 P1 Rt it? g5; Ywld gggg Kw. PD R35 .550

GzHfl- 5 Y 5 V v Inches 225 5.25 80.4 18.3 3.5 11.5 25 55 340 3 2, 940 225 54.78 59.5 55.3 1.0 1.7 115 10 500 3 1, 970 228 4.41 15.1. 10.5 2.4 15.9 4 1.55 50 400 4 2,495- 230 3.78 72.5 55.7 l4 .8 20.4 2 218 90 400 4 2,495 232 4.10 94:8 75.5 18.4 18.7 2 375 20 200 4 4, 990 233 3. 81 95.0 75.4 10. 20.1 2 325 20 200 4, 445 235 5. 9 97.7 82.5 13.9 14.2 4 50 20 100 5 9,995 237 4. 40 93:7 75.2 15.7 17.8 4 29 20 100 5 was 238 9.86 99.0 89.4 9.1 9.2 4 53 20 150 5 5,552 239 4.45 45.8 35.6 .0 17.7 1% 3 44 155 5 5,051 240 4.04 45.0 84.7 8.6 19.1 1 180 84" 240 8 4,158 241 4. 50 95.3 77.8 15.5 17.4 8 148 30 150 5; 227

in the form of successive pulses. The time be- More complete identification 0f the above coltween pulses, or repetition time, is determined by 2r umns is as follows: the voltage of the power supply and resistance 0 Sample r of sample that was 24. The amplitude of the current pulse deteranalyzed by m s spectrometer. mined by the potential appl ed to the condenser (2) v ratio by volum of hydrogen and the reactance' of the electrode c1rcu1t durmg formed to acetylene in the product Stream. (them the discharge p rectically 3 to 1).

An examlnatlon of the current. pulse when (3) Percent CH4 conv.percent of methane placed on a cathode ray oscilloscope disclosed converted that there is superimposed thereon a' current of (4) e r e Cf hydrogen radio frequency as shown in the curve marked mproduct stream (5) Percent C2H2volume percent of acetylene Curve E of Figure 2 has been plotted with elecin product m; trode voltage as ordinates and a i s (6) 181501 5515015.5551 yield on recycle basis. The electrode voltage represents instantaneous (7) Reaction a 1ength rea.cti0n path values of charged potential of condenser 2 I. length Obviously the device 0 Figure 1, roy P Q (8) Pk. kw.--pe'ak power in kilowatts; selection of materials for 1tems ll], II and I2, may (9) Pmmessure mm. of mercury mu1ti be built to withstand any desired internal pres-- plied by electrode spacing in centimeters sure. e V r V I (l0) Rep; ratepulse repetition rate per sec- In the operation of the above descrlbed appa 0nd. Ffi a reactant/such {methane i s ss sst (1 1) Pulse seer-length of pulse in microsec- 1s caused to flow slowly into the reaction chamher through the inlet 15 and traverse the reaction (12) Rest sap-rest duration between pulses zone between the electrodes 13' and [4 while pulse i m cr discharges are occurring between the electrodes. Alth h th b a 3 d t The energy pulses cause the methane to be cont th q a. a We mac ca'rne a verted into other products which are drawn ofi e m 6 pressure expenments Show a the process is operable up to and as much as two throughthe outlet l8. t h b t h 1 An example of such reactions is as follows: mosp fires We mosp t pressure.

- A mod fied form of electromc reactor is shown Methane'acetl/Zene reaction in Figure 3. This reactor comprises a base 2'! on Run number EP169 which is mounted a jacket or hood 28. Hood 28 Gas pressure, mm. Hg 1,0 forms With base 21 a pressure seal. A gas inlet Gas inlet temp, F 90 pipe 29 passes through the base 21 at 30 and Crest volta 4000 connects to a manifold block 3! carried by the Repetition interval,-millisec 50 ase 27. Manifold. 3| is provided with a. single v inlet passageway 32, which registers with the pipe volume 29, and a plurality of outlet passageways 33 Pro-duct Analysis Pe oent Weight which serve to distribute reactants introduced 95 Per Cent into the primary stage of the reactor.

0 Supported on manifold 31 are a series of elec- Methane 7 SA trodes 34, 35, 36 and 31 which are vertically sepajf e e rated by insulators 38, 39, 40 and 41, which also j fififi i ifj j 1 serve to direct the flow of gas through the pas- Pthane 0.4 1.7 sageways 42 formed in the electrodes 34 to 31, N itfsg taiin and through the reaction zones 43 to 46 inclu- Total 7 100 0 100 0 sive. The reaction products which are collected in the space 4'! flow from the reactor through Estimated Conversio'rz CH2 Recycled to Ezthe outlet ip 48 H2 and o2rraction -ff fi'i'f- 77 Electrodes 34 to 3'! inclusive may be formed of f brass, copper, or other electrical conductive ma-.

trial.

Electrical connection is made to the electrodes 34 to 31 by means of conductors 48, 49, 50 and 5|, which extend from outside the reactor through openings 52 in the base which are provided with insulating bushings 53, 54, 55 and 56.

The electrical circuit diagram for supplying power to electrodes 34 to 31 is shown in Figure 4. The electrical circuit for this form of reactor is similar to that used in connection with the reactor of Figure 1, differing only in that the electrodes SI to S6 themselves form the capacity. Alternate electrodes are connected together to form two groups of electrodes. One group, comprising electrodes S2, S4 and S6, is connected to one side of the power source not shown by conductor 51 and to ground at 58. The other side of the power supply is connected to each of the electrodes S1, S3 and S5 of the other group through conductors 62, 63 and 64, resistances 59, 60 and 6 I, and inductances 65, 66 and 61.

The source of power may be direct current of from 400 to 4000 volts, or resistors 59, 60 and GI may be connected to an alternating current 3 phase Y, the neutral of which is grounded at 58.

Inductances 65, 66 and 61 serve to control the rate of potential rise across the electrodes effecting a reduction in power loss over that which would be effected if resistors alone were employed.

When using direct current power the pulses are of the same character as those illustrated in connection with the reactor of Figure 1. This design permits the achievement of higher operating frequencies through the use of smaller capacities and a reduction in the direct current resistance of the discharge current path.

When using alternating current power the action is similar except that the discharge is forced to occur at a frequency which is a harmonic of the power supply frequency and that when high repetition rates are employed the supply voltage will vary at the supply frequency.

The pulse characteristics are controlled in the same manner as that .described in connection with the reactor of Figure 1. 7

In the operation of the form of reactor shown in Figur 3 a reactant such as methanein gaseous state is admitted to the reactor through pipe 29 and manifold 3| and is caused to pass upwardly through the passageways in the electrodes thereb traversing the successive reaction zones while energy pulses are being fed to the electrodes to produce a discharge between electrodes. In the reaction zones the methane is converted into other products.

An example of a reaction carried out in this type of reactor is as follows:

M ethanehydrogen reaction Run number EP184 Gas pressure, mm. Hg 1.5-2

Gas inlet temp, F 90 Crest voltage 350 Repetition interval, milliseconds i 0.002

Volume Per Cent Weight- (Mole Per Cent Per Cent) Methane 46.8

Hydrogen a 45.0

Acetylene l. 9

Ethylene .0. 9

Ethane 2. 3

Nitrogen- 3. 1

High Boiling Material Condensed The above results show approximately 50% conversion of methane to hydrogen in a single pass. Obviously by recycling the unconverted methane greater yield can be obtained.

The potential and pressure ranges employed are essentially those described in connection with the reactor of Figure 1.

Still another embodiment of an electronic reactor is shown in Figure 5. This form of reactor comprises an outer cylindrical housing 68 formed of an electrical conducting material. Housing 69 also serves as one electrode of the reactor. An inner cylindrical electrode 69 is concentrically spaced from the outer electrode. These two electrodes define a reaction zone 10 into which reactants are admitted in gaseous state through the inlet pipe ll located near the bottom of the outer electr0de'68. A product outlet 12 is located near the top of. the reactor as shown.

Direct current potential from a source not shown is applied across the electrodes by means of conductors I3, 14, resistance 15, conductor 16, the coaxial cable 11, and the tapered link 18. This potential may range from 50 to 4000 volts. The reason for the wide range of voltage will become apparent as the description proceeds.

The reactor of Figure 5 as described to this point will operate successfully in the manner pointed out in connection with the reactors of Figures 1 and 3. However, such operation requires a substantial potential across the electrodes to produce the desired discharge. In or.- der to overcome this undesirable feature means are provided for supplying a high voltage pulse having a definite repetition rate to the electrodes to initiate the discharge. The pulse generator is shown in Figure 5 as a block 19. Since pulse generators suitable for this purpose are well known in the art and no novelty is claimed for it, it will not be described in detail.

The pulses produced by the generator 19 may be of the form shown in Figure 7 or they may take the form of radar pulses as shown in Figure 8. Although the pulses of Figure 7 are shown of a single polarity it is obvious that alternate pulses can be of opposite polarity. Whenradar type pulses are used the generator 19 may comprise the elements indicated in the block diagram of Figure 6.

As pointed out above these pulses, which are conducted to the electrodes of the reactor through the coaxial cable 80, direct current isolation condenser BI and the tapered link 18, may be used merely to initiate the discharge between electrodes. Once a few ions are formed in the reaction zone a lower direct current voltage will supply the energy for the reaction. In this case the crest voltage of the pulse generator must be several times that of the direct current supply.

When using high frequency radar pulses of the type illustrated in Figure 8 a careful impedance matchmust be made between the coaxial transmission line 80 and the electrodes 68 and 69. To effect a proper match the top of the housing 68 is preferably tapered such that the tapered portion 7 is several wave lengths long. A corresponding taper which varies in the amount of taper, depending upon the impedance match sought, is given to the connecting link 18. The terminating impedance, that is, the load is chosen to give the optimum utilization of radio frequency energy and to achieve the desired reaction.

' The flexibility of the system illustrated in Figure 5 makes a further mode of operation possible. The direct current potential can be entirely removed and all of the reaction energy, in

the form of pulses, supplied by the pulse generator 19. This mode of operation is advantageous in carrying out certain types of reactions in which it i desired to follow the short period of time during which energy is supplied to the reaction by a rest period of predetermined length.

A still further mode of operation is desirable for certain types of reactions. The major portion of the energy for the reaction can be furnished by the pulse generator I9 and a small 1 direct current holding voltage supplied from the direct current source. The direct current holding voltage will function to maintain a continuous discharge between pulses which it is believed prevents recombination of the ions formed during the high energy pulse or controls the rate of recombination.

Examples of reactions carried out with the reactor of Figure are as follows:

Run number EP 160 Gas pressure, mm. Hg 1.0 Gas inlet temp, F 90 Crest voltage 350 Repetition interval, milliseconds 5.5

Volume Per Cent Weight (Mole Per Cent Per Cent) Methane 67. 7 78. 28 23.4 3.38 2.1 3.94 2.5 5.00 Ethane", 4. 3 9. 32

Total 100 99. 92

Run number EP.161 Gas pressure, mm. Hg 1.0 Gas inlet temp., "F 90 Crest voltage 350 Repetition interval, milliseconds 133 Volume Per Cent Weight (Mole Per Cent Per Cent) 68.9 79.88 22.9 3.31 2.3 4.33 Ethy1ene. 2. 5 5. 07 Ethane 3. 4 7. 39

Total 100 99. 98

The above examples are the results of a single pass through the reactor. The yield of products can be enhanced by recycling a part or all of the discharge products, or in a manner well known in the art, separation of the products can be effected and the unreacted methane recycled. This feature is in part illustrated in Figure 5 in which a recycling pump 82 connected in the tube or pipe line 83 may feed discharge products from the reactor to the inlet H by the proper manipulation of the valves 84 and 85.

Another example of a chemical reaction which has been carried out in a reactor of the general type as those described above is as follows:

Run number EP 324 Gas pressure, mm. of mercury 110 Gas inlet temp, "F 90 Crest voltage 5000 Repetition rate per second 1900 Length of pulse in microseconds 1.0

Volume per cent (mole per cent) Hydrogen 69.5 Ethane .2 Ethylene .9 Acetylene 12.0 Nitrogen 1.1 Methane 16.3

It is to be understood that the present invention is not to be limited to the specific examples recited above but has broad application in the chemical field.

I claim:

1. A method of converting methane into lower molecular weight hydrocarbons that comprises r subjecting the methane to a succession of pulses of ionizing electrical energy, each of said pulses having a substantially square wave form and aduration of from 0.1 to 2500 microseconds and followed by a rest period of substantially greater duration.

2. A method of converting methane into lower molecular weight hydrocarbons that comprises subjecting the methane to a succession of pulses of ionizing electrical energy, each pulsehaving a duration of from 0.1 to 2500 microseconds followed by a rest period of substantially greater duration.

3. A method of converting methane into lower molecular weight hydrocarbons that comprises subjecting the methane to a succession of pulses of ionizing electrical energy, each of said pulses having a wave form of high frequency and a duration of from 0.1 to 2500 microseconds and followed by a rest period of substantially greater duration.

4. A method of converting hydrocarbons in the gas phase that comprises subjecting the hydrocarbons while in the gas phase to a succession of pulses of ionizing electrical energy, each pulse having a duration of from 0.1 to 2500 microseconds followed by a rest period of substantially greater duration.

CARLETON H. SCHLESMAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,570,209 De Brey Jan. 19, 1926 1,838,374 Eddy Dec. 29, 1931 1,977,155 Stadler et a1. Oct. 16, 1934 2,000,224 Eisenhut May 7, 1935 2,072,917 Woelflin Mar. 9, 1937 2,080,933 Rose May 18, 1937 2,096,774 Wolfe Oct. 26, 1937 2,105,614 Roberts Jan. 18, 1938 2,257,177 Luster Sept. 30, 1941 2,279,583 Slayter Apr. 14, 1942 2,353,770 Suits July 18, 1944 FOREIGN PATENTS Number Country Date 296,355 Great Britain May 2, 1929 

4. A METHOD OF CONVERTING HYDROCARBONS IN THE GAS PHASE THAT COMPRISES SUBJECTING THE HYDROCARBONS WHILE IN THE GAS PHASE TO A SUCCESSION OF PULSES OF IONIZING ELECTRICAL ENERGY, EACH PULSE HAVING A DURATION OF FROM 0.1 TO 2500 MICRO- 